Synthesis of (±)-8-deisopropyladunctin B

(±)-8-Deisopropyladunctin B, the deisopropyl form of adunctin B, which was isolated from the leaves of Piper aduncum (Piperaceae) collected in Papua New Guinea, was synthesized in 0.77% overall yield in 17 steps from 5,7-dimethoxycoumarin-3-carboxylate. The key step was our original stereoconvergent skeleton transformation from 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-one to 1,2,4a,9b-tetrahydrodibenzofuran-4-ol with dimethylsulfoxonium methylide.     

Flower-like surface modification of titania materials by lithium hydroxide solution

Surface modification of titania materials to give flower-like structures has been achieved simply by the treatment in lithium hydroxide aqueous solution under mild conditions. The flower-like structured materials were characterized by X-ray diffraction, thermogravimetric analysis, and Raman scattering. The analyses indicate that the flower-like materials are composed of layered hydrous lithium titanate. It is suggested that the unique intercalation behavior of lithium ions into titania allows dissolution and re-precipitation of titania to form the flower-like structure. The obtained flower-like structure can be retained up to 700 °C, while the crystal phase transforms into Li(4)Ti(5)O(12).     

Experimental and theoretical analyses of azulene synthesis from tropones and active methylene compounds: reaction of 2-methoxytropone and malononitrile

A representative azulene formation from an active troponoid precursor (2-methoxytropone) and an active methylene compound (malononitrile) has been analyzed both experimentally and theoretically. (2)H-Tracer experiments using 2-methoxy[3,5,7-(2)H(3)]tropone (2-d(3)) and malononitrile anion give 2-amino-1,3-dicyano[4,6,8-(2)H(3)]azulene (1-d(3)) in quantitative yield. New and stable (2)H-incorporated reaction intermediates have been isolated, and main intermediates have been detected by careful low-temperature NMR measurements. The detection has been guided by mechanistic considerations and B3LYP/6-31(+)G(d) calculations. The facile and quantitative one-pot formation of azulene 1 has been found to consist of a number of consecutive elementary processes: (a) The troponoid substrate, 2-methoxytropone (2), is subject to a nucleophilic substitution by the attack of malononitrile anion (HC(CN)(2)(-)) to form a Meisenheimer-type complex 3, which is rapidly converted to 2-troponylmalononitrile anion (5). (b) The anion 5 is converted to an isolable intermediate, 2-imino-2H-cyclohepta[b]furan-3-carbonitrile (6), by the first ring closure in the reaction. (c) A nucleophilic addition of the second HC(CN)(2)(-) toward the imine 6 at the C-8a position produces the second Meisenheimer-type adduct 7. (d) The second ring closure leads to 1-carbamoyl-1,3-dicyano-2-imino-2,3-dihydroazulene (11). A base attacks the imine 11, which results in generation of a conjugate base 12 of the final product, azulene 1.     

Studies on rotational barriers of N-C axially chiral compounds: increase in the rotational barrier by aromatization

The rotational barriers in axially chiral quinolin-2-one and quinazolin-2-one possessing N-(ortho-tert-butyl)phenyl group were found to significantly increase in comparison with those of corresponding dihydroquinolin-2-one and dihydroquinazolin-2-one. Analysis of transition state structure during N-Ar bond rotation based on DFT calculation indicates that the increase in the rotational barrier is due to considerable distortion of the nitrogen-containing heterocyclic part.     

Cation‐Tuned Stimuli‐Responsive and Optical Properties of Supramolecular Hydrogels

Hierarchical self‐assembly of an amphiphilic tris‐urea in aqueous media is shown. A mixture of the amphiphilic tris‐urea and an alkaline solution gave a viscous solution composed of fibrous aggregates. This viscous solution transformed into supramolecular hydrogels, which are capable of hierarchically organizing into higher‐order aggregates in response to several cationic triggers. The resulting supramolecular hydrogels were relatively stiff and their storage moduli attained over 10³ Pa. The stimuli‐responsive and optical properties of the resulting hydrogels were influenced by the cationic trigger. Proton and calcium ion triggers gave pH‐ and chemical stimuli‐responsive hydrogels, respectively. A terbium ion trigger also provided a highly luminescent hydrogel through energy transfer from the tris‐urea to terbium.     

Spectroscopic study of antileishmanial drug incubated in the promastigotes of Leishmania mexicana

In this work we present spectroscopic study of Boldine (aporphine alkaloid) that possesses important biological activities, in particular, in interaction with the promastigotes of Leishmania mexicana. The results show the applicability of autofluorescence of this drug to determinate the possible mechanism of its biological action. The blue shift and hyperchromic effect in the emission spectrum of the drug in interaction with the parasite cells indicate an energy transference process between them. The morphological change of cell shape of the promastigotes treated with the drug is observed using confocal microscopy. This morphological cell-shape transformation evidences an important interaction between the drug studied and some protein of the parasite cell. Here we describe for the first time the fluorescence properties of the Boldine in the promastigotes of L. mexicana.     

A Linear programming formulation for routing asynchronous power systems of the Digital Grid

In recent years, practical research related to distributed power generation and networked distribution grids has been increasing. This research uses a relatively abstract model for the cost reduction in the Digital Grid Power Network. In the Digital Grid, the traditional wide-area synchronous grid is divided into smaller segmented grids which are connected asynchronously. In this paper, we demonstrate how to formulate the minimized cost of power generation by using linear programming methods, while considering the cost of electric transmission and distribution and using asynchronous power interchange among separate grids.     

Failure diagnosis of organic photovoltaic using electro-optic probe

This paper describes the measurement of an organic photovoltaic using an electro-optic probe. We verify the validity of the electro-optic probe by comparing it with a conventional electric probe. The electric field distribution of the organic photovoltaic is examined on the basis of results of the test board measurement using the electro-optic probe and results of the test board simulation using an electromagnetic field simulator. We succeed in failure diagnosis of the organic photovoltaic in three failure modes. We found that the organic photovoltaic has a failure cell, and the electro-optic probe is successfully applied to failure diagnosis of organic photovoltaic.     

Stable standing waves of nonlinear Schrödinger equations with a general nonlinear term

The orbital stability of standing waves of nonlinear Schrödinger equations with a general nonlinear term is investigated in this paper. We study the corresponding minimizing problem with L ²-constraint: $$E_\alpha = \inf\left\{\frac{1}{2}\int\limits_{\mathbb{R}^N} |\nabla u|^2 dx - \int\limits_{\mathbb{R}^N} F(|u|) dx; u \in H^1(\mathbb{R}^N), \|u\|_{L^2(\mathbb{R}^N)}^2=\alpha\right\}.$$ We discuss when a minimizing sequence with respect to E _α is precompact. We prove that there exists α ₀ ≥ 0 such that there exists a global minimizer if α > α ₀ and there exists no global minimizer if α < α ₀. Moreover, some almost critical conditions which determine α ₀ = 0 or α ₀ > 0 are established, and the existence results with respect to ${E_{\alpha_0}}$ under some conditions are obtained.